The present invention relates to a color photographic art. Particularly, it relates to a color image-forming method that is able to accomplish considerable improvement in simplification (convenience) of processing by the use of a silver halide color photographic light-sensitive material that is excellent in coloring property, storage stability, dye image fastness and hue, and moreover by omitting a conventional washing step and desilvering step.
Generally in a color photographic light-sensitive material, when the said light-sensitive material is exposed to light imagewise, then, in color-developing step, an oxidized p-phenylenediamine derivative reacts with a coupler to form an image. In this system, color reproduction by the subtractive color technique is used, and, to reproduce blue, green, and red colors, dye images of yellow, magenta, and cyan in color, respectively complementary to blue, green, and red, are formed.
Color development is accomplished by immersing (dipping) an exposed color photographic light-sensitive material in an alkaline aqueous solution containing a p-phenylenediamine derivative (a color developer).
The color image-forming method using a color photographic light-sensitive material excelled in that an image could be provided at a low price and in large quantities. On the other hand, the method had a drawback that an image formation could not be completed unless a bleach-fix step and a washing step were performed after the foregoing color-developing step. Consequently the processing apparatus inevitably became complicated and large in size.
Particularly in the case of a minilab or the like, by which a distributed processing is carried out, the apparatus must be of small size. Therefore, it is an essential condition to make compact and simplify the apparatus for the distributed processing of a photographic light-sensitive material.
The reason such latter steps must be performed, is that silver in a light-sensitive material is reduced by color development to a metal silver, which results in the metal silver remaining in the light-sensitive material. The remaining metal silver exhibits a black color, and therefore it deteriorates the purity of the color image. Consequently, it is necessary to remove the metal silver from the light-sensitive material. At the present time, the metal silver is removed from a light-sensitive material by means that the metal silver is converted to a silver ion, by bleach-fixing, and then the silver ion is removed together with an undeveloped silver halide, by fixing.
Examples of a method to omit such a bleach-fixing step from a processing include a method in which intensification processing with hydrogen peroxide is carried out, as described in, for example, the Journal of the Society of Photographic Science and Technology of Japan, Vol. 51, No. 3, p. 191 (1988), JP-B-61-48148 (xe2x80x9cJP-Bxe2x80x9d means examined Japanese patent publication), JP-B-63-20330, JP-B-63-20332, JP-A-3-111844 (xe2x80x9cJP-Axe2x80x9d means unexamined published Japanese patent application), and the like. Because an image amplified on a developed silver is formed by the intensification processing, a sufficient image density can be obtained, even though a light-sensitive material having remarkably reduction in silver content is used. Therefore, color stain due to a metal silver can be made negligibly small, so that bleaching and fixing are not needed.
However, a problem has arisen that a processing solution deteriorates with the lapse of time because of an oxidation-reduction reaction between peroxides, such as hydrogen peroxide used in intensification processing, and p-phenylenediamine derivatives.
To stabilize such a color developer for intensification, it is conceivable that the p-phenylenediamine derivative should be removed from the color developer.
Omission of the p-phenylenediamine derivatives from a color developer results in no color-formation. However, if the p-phenylenediamine derivative or the another compound having the same function, is incorporated in a light-sensitive material, there is no need to incorporate a p-phenylenediamine derivative in the processing solution. Examples of a method proposed in which a p-phenylenediamine derivative or another compound having the same function is incorporated in a light-sensitive material, include a method in which an aromatic primary amine or its precursor is built-in a light-sensitive material. Examples of the aromatic primary amine developing agent or its precursor, each of which can be built-in the light-sensitive material, include those as described in, for example, U.S. Pat. Nos. 2,507,114, 3,764,328, and 4,060,418, JP-A-56-6235, JP-A-58-192031, JP-A-11-106361, and JP-A-11-167185. Of these compounds, a compound that releases an aromatic primary amine upon a rearrangement reaction due to a peroxide, as described in JP-A-11-106361, JP-A-11-167185, and the like, is excellent in the compatibility of storage stability and coloring property. Another example of an effective means proposed is a method in which a stable color-forming reducing agent is built in a hydrophilic colloid layer, with examples of the reducing agent including hydrazine compounds as described in, for example, European Patent Nos. 0545491A1 and 0565165A1, JP-A-8-286340, JP-A-8-292529, JP-A-8-297354, JP-A-8-320542, and JP-A-8-292531; and sulfonamidophenol compounds as described in, for example, U.S. Pat. No. 4,021,240 and Research Disclosure No. 15108 (November 1976). These color-forming reducing agents have characteristics of excellent storage stability and high coloring property.
The reason the washing step is needed is that it is necessary to wash away ingredients that were originally incorporated in a light-sensitive material but have become unwanted to the light-sensitive material after image formation, and further it is much more necessary to wash away ingredients that were later brought into the light-sensitive material until completion of both the developing step and the bleach-fixing step but have become unwanted to the light-sensitive material after the image formation. Therefore, the need for such a washing step is greatly reduced if the bleach-fixing step is omitted. However, since the color developer is alkaline, unless a light-sensitive material that was passed through the color developer completes a bleach-fixing step or a washing step, the pH of a coated film of the light-sensitive material remains high, which has resulted in a considerable deterioration of the image stability after processing. Further, when a light-sensitive material having a silver amount lowered in a large margin is subjected to intensification processing, unless the light-sensitive material completes a fixing step or a washing step, a very small amount of silver still remains in the light-sensitive material. Consequently, such a very small amount of silver has caused a stain after the lapse of a long time.
Further, JP-A-58-127926 and the like discloses a method of processing a color-developed light-sensitive material with an acidic solution. JP-A-58-137837 discloses a method of processing a color-developed light-sensitive material with a solution containing a silver complex-forming agent.
However, even though these methods are used, there has been a need for an apparatus composed of a tank that is used to dip a light-sensitive material in a color developer; a supplemental tank that is used to stock a solution that replenish a color developer corresponding to the consumed amount thereof; a tank that is used to dip a color-developed light-sensitive material in an acidic solution; a supplemental tank that is used to stock a solution that replenish an acidic solution or a silver complex-forming agent-containing solution, corresponding to the consumed amount of each solution; and a waste solution tank, which is used to collect and stock an overflow solution and the like of the color developer, the acidic solution, and the silver complex-forming agent-containing solution. Consequently, the apparatus inevitably becomes large in size.
Further, when p-phenylenediamine derivatives are contained in a developer, the p-phenylenediamine derivatives from the developer are brought into an acidic solution by a running processing, and a decomposition product of the p-phenylenediamine derivatives accumulates therein. As a result, a problem has arisen that the above-mentioned decomposition products are brought into a light-sensitive material and then cause unequal stain streaks (unevenness).
On the other hand, as another method of making a: processing apparatus compact, there is a method of supplying a color developer or an activator solution (an alkaline solution substantially free of a color-developing agent) in the form of a thin layer. Examples of a method of supplying a processing solution in the form of a thin layer include a method of coating the processing solution in the form of a thin layer by a roller coat, a felt cloth, a sponge coat, and the like, as described in Japanese Patent No. 2,612,205 and the like, and a method of spraying a processing solution jetted from a thin nozzle, as described in, for example JP-A-6-324455, JP-A-9-179272, and JP-A-11-109582.
However in these methods, since the fixing step and the washing step are necessary in the latter step of the processing, tanks for these steps are needed. Therefore it has been difficult to completely simplify and miniaturize a processing apparatus even by these methods.
As to, in particular, a distributed processing of the light-sensitive material, it has been desired to develop an image-forming method capable of dissolving factors that make a processing apparatus become large sized as described above.
An object of the present invention is to provide a color image-forming method that is able to cope with both substantial improvement in the convenience of processing and simplification and miniaturization of a processing apparatus, and that causes less stain in the light-sensitive material after processing, by the use of a silver halide color photographic light-sensitive material that is excellent in coloring property, storage stability, dye image fastness and hue, and moreover by omitting a conventional washing step and desilvering step.
Other and further objects, features, and advantages of the invention will appear more fully from the following description, taken in connection with the accompanying drawings.